Effective removal of metal ions and cationic dyes from aqueous solution using different hydrazine-dopamine modified sodium alginate.

In this paper, DSA-AAD-DA and DSA-TPDH-DA were prepared to effectively remove metal ions and cationic dyes from aqueous solution. The hydrazone structure was prepared by hydrazide-modified SA which captured metal ions selectively, and the remaining functional groups were used as active adsorption sites for cationic dyes. The thermodynamic parameter for the sorption demonstrated the process is endothermic and spontaneous. In single process, the adsorption of metal ions by DSA-AAD-DA and DSA-TPDH-DA correlated well with the Freundlich model through the hydrazone structure coordination and ion exchange which was mainly chemical adsorption, and cationic dyes adsorption correlated well with the Langmuir model which was shown monolayer adsorption was dominant by hydrogen bonding, electrostatic interaction, and π-π interaction. In binary system, the mixed adsorption shown significant antagonism effect in high concentration, but cationic dyes and metal ions in low concentration were efficiently and simultaneously removed, the adsorption ability of DSA-TPDH-DA was much better than DSA-AAD-DA. Moreover, adsorption efficiency can still maintain more than 80% after five times adsorption-desorption recycle. Therefore, DSA-AAD-DA and DSA-TPDH-DA possessed great potential for wastewater treatment.

The Application of 2,6-Bis(4-Methoxybenzoyl)-Diaminopyridine in Solvent Extraction and Polymer Membrane Separation for the Recovery of Au(III), Ag(I), Pd(II) and Pt(II) Ions from Aqueous Solutions.

The work describes the results of the first application of 2,6-bis(4-methoxybenzoyl)-diaminopyridine (L) for the recovery of noble metal ions (Au(III), Ag(I), Pd(II), Pt(II)) from aqueous solutions using two different separation processes: dynamic (classic solvent extraction) and static (polymer membranes). The stability constants of the complexes formed by the L with noble metal ions were determined using the spectrophotometry method. The results of the performed experiments clearly show that 2,6-bis(4-methoxybenzoyl)-diaminopyridine is an excellent extractant, as the recovery was over 99% for all studied noble metal ions. The efficiency of 2,6-bis(4-methoxybenzoyl)-diaminopyridine as a carrier in polymer membranes after 24 h of sorption was lower; the percentage of metal ions removal from the solutions (%Rs) decreased in following order: Ag(I) (94.89%) > Au(III) (63.46%) > Pt(II) (38.99%) > Pd(II) (23.82%). The results of the desorption processes carried out showed that the highest percentage of recovery was observed for gold and silver ions (over 96%) after 48 h. The results presented in this study indicate the potential practical applicability of 2,6-bis(4-methoxybenzoyl)-diaminopyridine in the solvent extraction and polymer membrane separation of noble metal ions from aqueous solutions (e.g., obtained as a result of WEEE leaching or industrial wastewater).

Cinchona-alkaloid-based zwitterionic chiral stationary phases as potential tools for high-performance liquid chromatographic enantioseparation of cationic compounds of pharmaceutical relevance.

Enantiomers of cationic compounds of pharmaceutical relevance, namely tetrahydro-ß-carboline and 1,2,3,4-tetrahydroisoquinoline analogs, were separated by high-performance liquid chromatography. Separations were performed on Cinchona-alkaloid-based zwitterionic ion exchanger type chiral stationary phases applied as cation exchangers using mixtures of methanol and acetonitrile or tetrahydrofuran as bulk solvent components containing triethylammonium acetate or ammonium acetate as organic salt additives. On the zwitterionic ZWIX(+) and ZWIX(-) columns investigated, retention and enantioseparation of the studied basic analytes were influenced by the nature and concentration of the organic components of the mobile phase. The effect of organic salt additives on the retention behavior of the studied analytes can be described by the stoichiometric displacement model related to the counterion concentration. Investigations on the structure-retention relationships were performed applying different mobile phase systems for the two types of cationic analytes. For the thermodynamic characterization, parameters such as changes in standard enthalpy (Δ(ΔH°)), entropy (Δ(ΔS°)), and free energy (Δ(ΔG°)) were calculated on the basis of van't Hoff plots derived from the ln α versus 1/T curves. In most cases, enthalpy-driven enantioseparations were observed, with a consistent dependence of the calculated thermodynamic parameters on the mobile phase composition. Elution sequences of the studied compounds were determined in all cases.

Bioinspired Nucleophilic Attack on a Tungsten-Bound Acetylene: Formation of Cationic Carbyne and Alkenyl Complexes.

Inspired by the proposed inner-sphere mechanism of the tungstoenzyme acetylene hydratase, we have designed tungsten acetylene complexes and investigated their reactivity. Here, we report the first intermolecular nucleophilic attack on a tungsten-bound acetylene (C2H2) in bioinspired complexes employing 6-methylpyridine-2-thiolate ligands. By using PMe3 as a nucleophile, we isolated cationic carbyne and alkenyl complexes.

Simultaneous capillary electrophoresis of anions and cations in a single injection using an anion exchanger-modified capillary for determination of salivary ions in combination with statistical analyses.

This paper describes the simultaneous capillary electrophoresis (CE) of anions and cations using an anion exchange-modified capillary, which was prepared by chemical coating with a cationic silylating reagent, and its application to saliva analysis. The CE method provides high-throughput (5 min for a single sample injection) analysis by generating a high-velocity electroosmotic flow at pH 3.0-3.5. The detection limits at a signal-to-noise ratio of 3 ranged from 1.2 to 18 µM for anions and 1.0 to 2.7 µM for cations. The relative standard deviations for the migration times and peak areas of analytes (n = 4) ranged from 0.05% to 0.40% and 0.94% to 4.7%, respectively. The CE system was used to analyze 11 common ions in saliva samples collected from long-distance runners and sedentary university students before and after running for a set distance or a set time. Interestingly, the SCN- concentrations decreased in the saliva samples of all 14 athletes and 16 sedentary students after running. Furthermore, when the concentrations of the analyzed ions were compared with that of cortisol as a typical stress marker by multiple regression analysis, SCN- and NO3- in saliva samples from the two subject groups strongly correlated with cortisol levels, as determined by an electrochemiluminescence immunoassay. This study improves our knowledge of both the analytical methodology for CE and statistical methods for identifying common ions that could be used as physical stress markers.

Stepwise Ethanol-Water Fractionation of Enzymatic Hydrolysis Lignin to Improve Its Performance as a Cationic Dye Adsorbent.

In this work, lignin fractionation is proposed as an effective approach to reduce the heterogeneity of lignin and improve the adsorption and recycle performances of lignin as a cationic dye adsorbent. By stepwise dissolution of enzymatic hydrolysis lignin in 95% and 80% ethanol solutions, three lignin subdivisions (95% ethanol-soluble subdivision, 80% ethanol-soluble subdivision, and 80% ethanol-insoluble subdivision) were obtained. The three lignin subdivisions were characterized by gel permeation chromatography (GPC), FTIR, 2D-NMR and scanning electron microscopy (SEM), and their adsorption capacities for methylene blue were compared. The results showed that the 80% ethanol-insoluble subdivision exhibited the highest adsorption capacity and its value (396.85 mg/g) was over 0.4 times higher than that of the unfractionated lignin (281.54 mg/g). The increased adsorption capacity was caused by the enhancement of both specific surface area and negative Zeta potential. The maximum monolayer adsorption capacity of 80% ethanol-insoluble subdivision by adsorption kinetics and isotherm studies was found to be 431.1 mg/g, which was much higher than most of reported lignin-based adsorbents. Moreover, the 80% ethanol-insoluble subdivision had much higher regeneration yield (over 90% after 5 recycles) compared with the other two subdivisions. Consequently, the proposed fractionation method is proved to be a novel and efficient non-chemical modification approach that significantly improves adsorption capacity and recyclability of lignin.

Near field non-invasive electrophysiology of retrotrapezoid nucleus using amperometric cation sensor.

Central chemoreception is the process whereby the brainstem senses blood gas levels and adjusts homeostatic functions such as breathing and cardiovascular tone accordingly. Rodent evidence suggests that the retrotrapezoid nucleus (RTN) is a master regulator of central chemoreception, in particular, through direct sensation of acidosis induced by CO2 levels. The oscillatory dynamics caused by pH changes as sensed by the RTN surface and its relationship to the fluctuations in cation flux is not clearly understood due to the current limitations of electrophysiology tools and this article presents our investigations to address this need. A cation selective sensor fabricated from polypyrrole doped with dodecyl benzenesulfonate (PPy (DBS)) is placed over RTN in an ex-vivo en bloc brain and changes in cation concentration in the diffusion limited region above the RTN is measured due to changes in externally imposed basal pH. The novelty of this technique lies in its feasibility to detect cation fluxes from the cells in the RTN region without having to access either sides of the cell membrane. Owing to the placement of the sensor in close proximity to the tissue, we refer to this technique as near-field electrophysiology. It is observed that lowering the pH in the physiological range (7.4-7.2) results in a significant increase in cation concentration in the vicinity of RTN with a median value of ~5 µM. The utilization of such quantifiable measurement techniques to detect sub-threshold brain activity may help provide a platform for future neural network architectures. Findings from this paper present a quantifiable, sensitive, and robust electrophysiology technique with minimal damage to the underlying tissue.

Trimellitated sugarcane bagasse: A versatile adsorbent for removal of cationic dyes from aqueous solution. Part II: Batch and continuous adsorption in a bicomponent system.

In the second part of this series of studies, the bicomponent adsorption of safranin-T (ST) and auramine-O (AO) on trimellitated sugarcane bagasse (STA) was evaluated using equimolar dye aqueous solutions at two pH values. Bicomponent batch adsorption was investigated as a function of contact time, solution pH and initial concentration of dyes. Bicomponent kinetic data were fitted by the pseudo-first-order and pseudo-second-order models and the competitive model of Corsel. Bicomponent equilibrium data were fitted by the real adsorbed solution theory model. The antagonistic interactions between ST and AO in the adsorption systems studied contributed to obtain values of maximum adsorption capacity in mono- (Qmax,mono) and bicomponent (Qmax,multi) lower than unity (Qmax,multi/Qmax,mono at pH 4.5 for ST of 0.75 and AO of 0.37 and at pH 7 for ST of 0.94 and AO of 0.43). Mono- and bicomponent adsorption of dyes in a fixed-bed column was evaluated at pH 4.5. The breakthrough curves were fitted by the Thomas and Bohart-Adams original models. Desorption of ST in a fixed-bed column was studied. The results obtained from the bicomponent batch and continuous adsorption showed that the presence of ST most affected the AO adsorption than the presence of AO affected the ST adsorption.

Modulation of cation trans-membrane transport in GO-MoS2 membranes through simultaneous control of interlayer spacing and ion-nanochannel interactions.

The interlayer spacing and ion-nanochannel interactions of graphene oxide membranes (GOMs) were simultaneously modulated by thermal reduction and mixing with MoS2 flakes for realizing selective ion separation, which was evaluated by the ratio of ion trans-membrane penetration rates (IPR). The results showed that the ratio of IPRCu2+ to IPRNa+ increased to 1.90 in GOM after thermal reduction for 5 h, which was ∼9.56 times higher than that without thermal reduction, indicating the increase of selectivity of Cu2+ over Na+. This was because the reduction of oxygen-containing groups narrowed the interlayer spacing and moderated the coordination between Cu2+ and sp3 clusters in GO, leading to an enhancement of the size-sieving effect but a decrease in the Cu (II)-nanochannel interaction. Meanwhile, the value of IPRCu2+/IPR Na+ was 0.374 after intercalating MoS2 into GO laminates (GO-MoS2 membrane, GMM), which was ∼1.87 times higher in comparison with that in GOM. This might be because the intercalation of MoS2 narrowed the interlayer spacing, enhanced the size-sieving effect, and strengthened the Na+ ion-nanochannel interactions (cation-π and ion-MoS2 chemical interactions) according to density functional theory calculations. Furthermore, IPRCu2+/IPR Na+ was ∼5.09 in GMM under thermal reduction for 5 h, which was ∼25.5 times higher in comparison with that in GOM without thermal reduction, exhibiting a great enhancement in selectivity for Cu2+. This indicated that thermal reduction and MoS2 intercalation could work in concert to control the size-sieving effect and ion-nanochannel interactions to achieve fine separation of heavy metal ions from main group metal ions.

Unexpected separate elution of cation and anion of an ammonium salt in supercritical fluid chromatography.

Amines are frequently used as additives in supercritical fluid chromatography (SFC). They allow eluting basic analytes with reasonable retention times and less distorted peak shapes. Since amines are chemically active compounds, their introduction into SFC mobile phase always raises a question on whether they can react with analytes or mobile phase constituents and, if so, can it affect chromatography separation. Primary and secondary amines are known to react with carbon dioxide, also all amines, being bases, can interact with CO2-alcohol mixtures which are known to be slightly acidic. In this work, we report a case of separate elution of an ammonium salt, salbutamol sulfate, anion and cation in SFC. Retention time of a peak which molecular mass registered by mass-spectrometry in ES(-) mode corresponds to HSO4- differs substantially from the retention time of a peak corresponding to salbutamol [M+H] registered in ES(+) regime. Moreover, sulfate anion retention time depends both on amine additive type and concentration whereas salbutamol retention time doesn't. Similar effect is observed on other columns as well as with other ammonium salts. We suppose that such behavior is caused by the exchange chemical reaction happening between ammonium salt analyte and amine additive. An additive converts a salt into a free base form and turns into a salt form itself. If this hypothesis is true, it might be important to take the possibility of such interactions into account during preparative SFC work since the compound injected might not be equivalent to a compound eluted.

Injection system for fast capillary electrophoresis based on pressure regulation with flow restrictors.

A fast automated system for rapid electrophoretic separations in short conventional capillaries employing contactless conductivity detection is presented. The instrument is based on pneumatic pressurization and does not require a conventional pump. The required pressures and flow rates for the different steps of the injection and flushing processes are produced with the help of two flow restrictors. The device is implemented on a microfluidic breadboard with dimensions of ca. 13 × 20 cm and employs miniature valves. Nine inorganic cations, namely NH4+, K+ , Na+ , Ca2+ , Mg2+ , Mn2+ , Sr2+ , Li+ , and Ba2+ , could be separated in a capillary of 10 µm inner diameter and 6 cm effective length within 25 s. Following a reduction of the effective length to 4 cm, still five inorganic cations could be separated in a time span of 12 s. The repeatability of peak areas was better than 3.1 % and limits of detection between 3.5 and 5.5 µM were achieved.

Identification and characterization of multifunctional cationic peptides from traditional Japanese fermented soybean Natto extracts.

In this study, we investigated the lipopolysaccharide (LPS)-neutralizing and angiogenic activities of cationic peptides derived from the traditional Japanese fermented product Natto, which is made by fermenting cooked soybeans using Bacillus subtilis. Initially, we prepared 20 fractions of Natto extracts with various isoelectric points (pI's) using ampholyte-free isoelectric focusing (autofocusing). Cationic peptides were then purified from fractions 19 and 20, whose pH values were greater than 12, using reversed-phase high-performance liquid chromatography, and were identified using matrix-assisted laser/desorption ionization-time-of-flight mass spectroscopy. Among the 13 identified cationic peptides, seven (KFNKYGR, FPFPRPPHQK, GQSSRPQDRHQK, QRFDQRSPQ, ERQFPFPRPPHQK, GEIPRPRPRPQHPE, and EQPRPIPFPRPQPR) had pI's greater than 9.5, positive net charges, and differing molecular weights. These peptides were then chemically synthesized and applied to chromogenic LPS-neutralizing assays using Limulus amebocyte lysates, and 50% effective (neutralizing) concentrations of 2.6-5.5 µM were demonstrated. In addition, tube formation assays in human umbilical vein endothelial cells revealed angiogenic activities for all but one (GEIPRPRPRPQHPE) of these seven cationic peptides, with increases in relative tube lengths of 23-31% in the presence of peptides at 10 µM. Subsequent experiments showed negligible hemolytic activity of these peptides at concentrations of up to 500 µM in mammalian red blood cells. Collectively, these data demonstrate that six cationic peptides from Natto extracts, with the exception of GEIPRPRPRPQHPE, have LPS-neutralizing and angiogenic activities but do not induce hemolysis.

Siderophore coated magnetic iron nanoparticles: Rational designing of water soluble nanobiosensor for visualizing Al3+ in live organism.

This article aims to establish the judicious use of iron-binding chemistry of microbial chelators in order to functionalize the surface of iron nanoparticles to develop non-toxic nanobiosensor. Anchoring a simple siderophore 2,3-dihydroxybenzoylglycine (H3L), which bears catechol and carboxyl functionalities in tandem, on to the surface of Fe3O4 nanoparticles has developed a unique nanobiosensor HL-FeNPs which showed highly selective and sensitive detection of Al3+ in 100% water at physiological pH. The biosensor HL-FeNPs, with 20nM limit of detection, behaves reversibly and instantly. In-vivo bio-imaging in live brine shrimp Artemia confirmed that HL-FeNPs could be used as fluorescent biomarker for Al3+ in live whole organisms. Magnetic nature of the nanosensor enabled HL-FeNPs to remove excess Al3+ by using external magnet. To our knowledge, the possibility of microbial chelator in the practical development of Al3+ selective nanobiosensor is unprecedented.

Production of low-expressing recombinant cationic biopolymers with high purity.

The growing complexity of recombinant biopolymers for delivery of bioactive agents requires the ability to control the biomaterial structure with high degree of precision. Genetic engineering techniques have provided this opportunity to synthesize biomaterials in an organism such as E. coli with full control over their lengths and sequences. One class of such biopolymers is recombinant cationic biopolymers with applications in gene delivery, regenerative medicine and variety of other biomedical applications. Unfortunately, due to their highly cationic nature and complex structure, their production in E. coli expression system is marred by low expression yield which in turn complicates the possibility of obtaining pure biopolymer. SlyD and ArnA endogenous E. coli proteins are considered the major culprits that copurify with the low-expressing biopolymers during the metal affinity chromatography. Here, we compared the impact of different parameters such as the choice of expression hosts as well as metal affinity columns in order to identify the most effective approach in obtaining highly pure recombinant cationic biopolymers with acceptable yield. The results of this study showed that by using E. coli BL21(DE3) LOBSTR strain and in combination with our developed stringent expression and Ni-NTA purification protocols highly pure products in one purification step (>99% purity) can be obtained. This approach could be applied to the production of other complex and potentially toxic biopolymers with wide range of applications in biomedicine.

Dual-opposite injection capillary electrophoresis: Principles and misconceptions.

Dual-opposite injection capillary electrophoresis (DOI-CE) is a separation technique that utilizes both ends of the capillary for sample introduction. The electroosmotic flow (EOF) is suppressed to allow all ions to reach the detector quickly. Depending on the individual electrophoretic mobilities of the analytes of interest and the effective length that each analyte travels to the detection window, the elution order of analytes in a DOI-CE separation can vary widely. This review discusses the principles, applications, and limitations of dual-opposite injection capillary electrophoresis. Common misconceptions regarding DOI-CE are clarified.

Metal Ions Analysis with Capillary Zone Electrophoresis.

Capillary electrophoresis has recently attracted considerable attention as a promising analytical technique for metal ion separations. Significant advances that open new application areas for capillary electrophoresis in the analysis of metal species occurred based on various auxiliary separation principles. These are mainly due to complexation, ion pairing, solvation, and micellization interactions between metal analytes and electrolyte additives, which alter the separation selectivity in a broad range. Likewise, many separation studies for metal ions have been concentrated on the use of preelectrophoresis derivatization methodology. Approaches suitable for manipulation of selectivity for different metal species including metal cations, metal complexes, metal oxoanions, and organometallic compounds, are discussed, with special attention paid to the related electrophoretic system variables using illustrative examples.

Influence of milling on the adsorption ability of eggshell waste.

Eggshell waste was successfully used for the removal of heavy metal ions from model solutions. The effect of ball milling on the structure and adsorption ability of eggshell (ES) and its membrane (ESM) was investigated, with the conclusion that milling is benefitial only for the ES. The adsorption experiments showed that the ESM is a selective adsorbent, as the adsorption ability toward different ions decreased in the following order: Ag(I) > Cd(II) > Zn(II). The obtained Qm values for Ag(I) adsorption on the ESM and ES were 52.9 and 55.7 mg g(-1), respectively. The potential industrial application of ES was also demonstrated by successful removal of Ag(I) from the technological waste.

Simultaneous micro-electromembrane extractions of anions and cations using multiple free liquid membranes and acceptor solutions.

Micro-electromembrane extractions (µ-EMEs) across free liquid membranes (FLMs) were applied to simultaneous extractions of anions and cations. A transparent narrow-bore polymeric tubing was filled with adjacent plugs of µL volumes of aqueous and organic solutions, which formed a stable five-phase µ-EME system. For the simultaneous µ-EMEs of anions and cations, aqueous donor solution was the central phase, which was sandwiched between two organic FLMs and two aqueous acceptor solutions. On application of electric potential, anions and cations in the donor solution migrated across the two FLMs and into the two peripheral acceptor solutions in the direction of anode and cathode, respectively. Visual monitoring of anionic (tartrazine) and cationic (phenosafranine) dye confirmed their simultaneous µ-EMEs and their rapid (in less than 5 min) transfers into anolyte and catholyte, respectively. The concept of simultaneous µ-EMEs was further examined with selected model analytes; KClO4 was used for µ-EMEs of inorganic anions and cations and ibuprofen and procaine for µ-EMEs of acidic and basic drugs. Quantitative analyses of the resulting acceptor solutions were carried out by capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C(4)D). Good extraction recoveries (91-94%) and repeatability of peak areas (≤6.3%) were achieved for 5 min µ-EMEs of K(+) and ClO4(-). Extraction recoveries and repeatability of peak areas for 5 min µ-EMEs of ibuprofen and procaine were also satisfactory and ranged from 35 to 63% and 7.6 to 11.3%, respectively. Suitability of the presented micro-extraction procedure was further demonstrated on simultaneous µ-EMEs with subsequent CE-C(4)D of ibuprofen and procaine from undiluted human urine samples.

Electrokinetic sample preconcentration and hydrodynamic sample injection for microchip electrophoresis using a pneumatic microvalve.

A microfluidic platform was developed to perform online electrokinetic sample preconcentration and rapid hydrodynamic sample injection for zone electrophoresis using a single microvalve. The polydimethylsiloxane microchip comprises a separation channel, a side channel for sample introduction, and a control channel which is used as a pneumatic microvalve aligned at the intersection of the two flow channels. The closed microvalve, created by multilayer soft lithography, serves as a nanochannel preconcentrator under an applied electric potential, enabling current to pass through while preventing bulk flow. Once analytes are concentrated, the valve is briefly opened and the stacked sample is pressure injected into the separation channel for electrophoretic separation. Fluorescently labeled peptides were enriched by a factor of ∼450 in 230 s. This method enables both rapid analyte concentration and controlled injection volume for high sensitivity, high-resolution CE.

Metal-Ion Metathesis and Properties of Triarylboron-Functionalized Metal-Organic Frameworks.

An anionic metal-organic framework, H3[(Mn4Cl)3L8]⋅30H2O⋅2.5 DMF⋅5 Diox (UPC-15), was successfully prepared by the reaction of MnCl2 with tris(p-carboxylic acid)tridurylborane (H3 L) under solvothermal conditions. UPC-15 with wide-open pores (∼18.8 Å) is constructed by packing of octahedral and cuboctahedral cages, and exhibits high gas-sorption capabilities. Notably, UPC-15 shows selective adsorption of cationic dyes due to the anion framework. Moreover, the catalytic and magnetic properties were investigated, and UPC-15 can highly catalyze the cyanosilylation of aromatic aldehydes. UPC-15 exhibits the exchange of metal ions from Mn to Cu in a single-crystal-to-single-crystal manner to generate UPC-16, which could not be obtained by the direct solvothermal reaction of CuCl2 and H3L. UPC-16 exhibits similar properties for gas sorption, dye separation, and catalytic activity. However, the magnetic behaviors for UPC-15 and UPC-16 are distinct due to the metal-specific properties. Below 47 K, UPC-15 exhibits a ferromagnetic coupling but UPC-16 shows a dominant antiferromagnetic behavior.